EP0117912B1 - Process for producing lightly coloured polyesters by using titanium catalysts - Google Patents
Process for producing lightly coloured polyesters by using titanium catalysts Download PDFInfo
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- EP0117912B1 EP0117912B1 EP83112290A EP83112290A EP0117912B1 EP 0117912 B1 EP0117912 B1 EP 0117912B1 EP 83112290 A EP83112290 A EP 83112290A EP 83112290 A EP83112290 A EP 83112290A EP 0117912 B1 EP0117912 B1 EP 0117912B1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/87—Non-metals or inter-compounds thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
Definitions
- polyfunctional alcohols i.e. Diols, triols or polyols and polybasic carboxylic acids, i.e. To produce di-, tri- or polycarboxylic acids or their derivatives, amorphous or crystalline polyesters with properties adapted to the respective intended use.
- the first stage can be carried out as a transesterification reaction using lower alkyl esters, especially methyl esters of carboxylic acids, the second stage as an esterification reaction using or using carboxylic acids and the third as a polycondensation reaction. If no esters of carboxylic acids are used, production begins with the esterification.
- transesterification or esterification catalysts of zinc, cadmium, manganese or calcium either insufficiently accelerate the esterification or polycondensation reaction or in the ones required for the esterification or polycondensation reaction compared to the transesterification reaction or esterification reaction higher concentrations not only the polycondensation reaction, but also decomposition reactions with the consequence of, inter alia Cause discoloration.
- decomposition reactions with increasing content of decomposition products in the polycondensates, their performance properties deteriorate.
- the concentration of the transesterification and / or esterification catalysts is kept as low as is necessary for an undisturbed course of the respective reaction or the catalyst of the transesterification or esterification stage is deactivated after the reaction, for example by adding phosphorus compounds such as phosphoric acid , phosphorous acid, hypophosphorous acid, phosphinic acid or its esters or salts thereof, and the polycondensation is carried out after adding another catalyst.
- Suitable catalysts for the polycondensation are from R.E. Wilfang, I. Polymer Sci. 54 (1961) 388 in large numbers.
- Soluble antimony compounds are often used particularly for the polycondensation stage because of their good catalytic activity. However, they have the disadvantage of easily forming metallic antimony by reduction, which turns the polycondensate grayish.
- titanium compounds As polycondensation catalysts. According to H. Zimmermann, Faserforschung u. Textile technology 13 No. 11 (1962), 481 to 490, their catalytic activity is comparable to the antimony compounds and side reactions are not very troublesome.
- titanium compounds have the disadvantage of turning the polycondensates yellow-brown, especially with ethylene glycol as a component of the polyesters.
- the object was therefore to reduce the discoloration of the polycondensates caused by titanium catalysts and, if possible, to increase the effectiveness of titanium catalysts.
- the invention therefore relates to a process for the preparation of polyesters from polyfunctional alcohols and polybasic carboxylic acids and / or their alkyl esters and / or their anhydrides in the presence of catalytically active titanium compounds, in the presence of compounds of phosphorous acid and optionally other known transesterification, esterification - And polycondensation catalysts and other auxiliaries, characterized in that catalytic amounts of adducts of phosphorous acid and monoepoxides with molar ratios of the components of 1: 1, 1: 2 or 1: 3 are used as compounds of phosphorous acid.
- Triesters of phosphoric acid with glycols and from AT-B-263371 polyesters of glycols and phosphorous acid are known from EP-A 1 -6603 as stabilizers for improving the light and thermal stability of polyesters, but there is no increase in the effectiveness of Titanium catalysts described in the polyester formation.
- Titanium catalysts are understood to be any known titanium catalysts per se, preferably titanium esters of aliphatic or cycloaliphatic alcohols having 3 to 12, in particular 4 to 10, carbon atoms, such as butyl titanate and octyl titanate, and soluble titanium chelates made from, for example, 1,3-diols, in particular with 2 , 2,4-trimethylpentanediol - 1,3, 2-methylpentanediol-2,4 or 2-ethylhexanediol-1,3.
- the adducts used in addition to the titanium catalysts are particularly suitable for the esterification stage and to the same extent for the subsequent polycondensation stage. With their help, polyesters of low and particularly high degree of polycondensation can be produced.
- the adducts make it possible to produce light-colored polyesters with very low color numbers instead of highly discolored polyesters.
- the adducts increase the effectiveness of the titanium catalysts, so that the reaction time of the esterification is sometimes greatly shortened with increasing amount of adducts and with increasing amount of EpoxiQ8 in the adduct, the degree of condensation is increased and the completeness of the reaction, measurable with reduced carboxy numbers , Acid numbers or hydroxyl numbers, is increased. Of particular value is a reduction in the acid numbers in the finished polyester to very low values.
- the adducts cause a significant, sometimes very significant increase.
- the adducts are therefore preferably used in the esterification stage and subsequently in the polycondensation stage and thus make it possible to together with the titanium compound alone in the possibly preceding transesterification stage, the use of a single catalyst for the entire polyester production.
- the esterification in the esterification stage is much more complete than before, measured on the distilled water, before the polycondensation is initiated by increasing the temperature and reducing the pressure.
- the amount of adducts can be 0.2 to 1.8 g, preferably 0.3 to 1.5 g, of adduct per 0.001 g of titanium catalyst.
- the adducts can be prepared in inert solvents, but preferably without solvents, the particular monoepoxide being heated to temperatures of up to 200 ° C., preferably 70 to 100 ° C., in a round-bottomed flask with a column attached, under a nitrogen atmosphere.
- the phosphorous acid preferably as 99% phosphorous acid, is added in portions or continuously, cooling being necessary if necessary due to exothermic reactions. A post-reaction time at temperatures of 60 to 90 ° can follow.
- Adducts with molar ratios of phosphorous acid and monoepoxide of 1: 1.1: 2 or 1: 3 are produced and used.
- Any known monoepoxides are suitable as monoepoxides, in particular the glycidyl esters of aliphatic or cycloaliphatic carboxylic acids, the glycidyl ethers of monoalcohols and optionally alkylphenols, and also alkene oxides and optionally cycloalkene oxides with preferably 5 to 10 carbon atoms.
- Monoepoxides with relatively high boiling points are preferred.
- Preferred epoxides are glycidyl esters of fatty acids with 6 to 15 carbon atoms.
- the glycidyl ester from branched-chain saturated fatty acids of a mixture with 8 to 10 carbon atoms is briefly referred to in the examples as “PC” with the addition of the molar ratios (“Cardura E.” @ Shell).
- the components of the mixed polyesters produced according to the process can contain all known aliphatic, cycloaliphatic or aromatic diols, if appropriate triols and polyols, and aliphatic, cycloaliphatic or aromatic dicarboxylic acids as well as if appropriate tri- and polycarboxylic acids and their derivatives, in particular their esters of Ci to C 4 -Alcohols and their anhydrides include.
- the melting point peak (Ts), the recrystallization peak (T R ) and the glass point (TG) were determined using a differential calorimeter, model DSC 1 from Perkin-Elmer.
- the end group concentration is determined by acid number SZ, hydroxyl number OHZ, both in mg KOH / g, or the carboxyl number (C) in mVaLCOOH / kg polymer according to H. Pohl, Analytic. Chem. 26 (1954), 1614.
- the Gardner color number (GFZ) of the flowable or melted polyester was determined in accordance with DIN 6961.
- the product obtained had the following key figures: ⁇ red. 0.225, SZ 18, OHZ 37 and GFZ 9.
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Abstract
Description
Es ist bekannt, aus mehrfunktionellen Alkoholen d.h. Diolen, Triolen bzw. Polyolen und mehrbasischen Carbonsäuren, d.h. Di-, Tri- bzw. Polycarbonsäuren oder deren Derivaten, amorphe oder kristalline Polyester mit dem jeweiligen Verwendungszweck angepassten Eigenschaften herzustellen.It is known to use polyfunctional alcohols, i.e. Diols, triols or polyols and polybasic carboxylic acids, i.e. To produce di-, tri- or polycarboxylic acids or their derivatives, amorphous or crystalline polyesters with properties adapted to the respective intended use.
Erfolgt eine mehrstufige Synthese, so kann die erste Stufe als Umesterungsreaktion unter Einsatz von Niedrigalkylestern, besonders Methylestern der Carbonsäuren, die zweite Stufe als Veresterungsreaktion unter Einsatz oder Mitverwendung von Carbonsäuren und die dritte als Polykondensationsreaktion ausgeführt werden. Werden keine Ester von Carbonsäuren verwendet, beginnt die Herstellung mit der Veresterung. Jede dieser Stufen erfordert im Regelfalle verschiedene Katalysatoren, da die Umesterungs- bzw. Veresterungskatalysatoren des Zinks, Cadmiums, Mangans oder Calciums entweder die Veresterungs- oder die Polykondensationsreaktion nur unzureichend beschleunigen oder in den für die Veresterungs- oder Polykondensationsreaktion erforderlichen, im Vergleich zu der Umesterungsreaktion oder Veresterungsreaktion höheren Konzentrationen nicht nur die Polykondensationsreaktion, sondern auch Zersetzungsreaktionen mit der Folge von u.a. Verfärbungen bewirken. Mit steigendem Gehalt an Zersetzungsprodukten in den Polykondensaten verschlechtern sich aber deren Gebrauchseigenschaften.If a multi-stage synthesis takes place, the first stage can be carried out as a transesterification reaction using lower alkyl esters, especially methyl esters of carboxylic acids, the second stage as an esterification reaction using or using carboxylic acids and the third as a polycondensation reaction. If no esters of carboxylic acids are used, production begins with the esterification. Each of these stages generally requires different catalysts because the transesterification or esterification catalysts of zinc, cadmium, manganese or calcium either insufficiently accelerate the esterification or polycondensation reaction or in the ones required for the esterification or polycondensation reaction compared to the transesterification reaction or esterification reaction higher concentrations not only the polycondensation reaction, but also decomposition reactions with the consequence of, inter alia Cause discoloration. However, with increasing content of decomposition products in the polycondensates, their performance properties deteriorate.
Deshalb wird nach dem Stand der Technik die Konzentration der Umesterungs- und/oder Veresterungskatalysatoren so niedrig gehalten, wie für einen ungestörten Verlauf der jeweiligen Reaktion erforderlich oder der Katalysator der Umesterungs- bzw. Veresterungsstufe nach der Umsetzung desaktiviert, beispielsweise durch Zugabe von Phosphorverbindungen wie Phosphorsäure, phosphoriger Säure, unterphosphoriger Säure, Phosphinsäure oder deren Ester bzw. deren Salze, und die Polykondensation nach Zugabe eines anderen Katalysators ausgeführt.Therefore, according to the prior art, the concentration of the transesterification and / or esterification catalysts is kept as low as is necessary for an undisturbed course of the respective reaction or the catalyst of the transesterification or esterification stage is deactivated after the reaction, for example by adding phosphorus compounds such as phosphoric acid , phosphorous acid, hypophosphorous acid, phosphinic acid or its esters or salts thereof, and the polycondensation is carried out after adding another catalyst.
Geeignete Katalysatoren für die Polykondensation sind aus R.E. Wilfang, I. Polymer Sci. 54 (1961) 388 in grosser Zahl bekannt. Lösliche Antimonverbindungen werden wegen guter katalytischer Wirkung häufig besonders für die Stufe der Polykondensation verwendet. Sie haben aber den Nachteil, leicht durch Reduktion metallisches Antimon zu bilden, das das Polykondensat graustichig verfärbt.Suitable catalysts for the polycondensation are from R.E. Wilfang, I. Polymer Sci. 54 (1961) 388 in large numbers. Soluble antimony compounds are often used particularly for the polycondensation stage because of their good catalytic activity. However, they have the disadvantage of easily forming metallic antimony by reduction, which turns the polycondensate grayish.
Verbindungen anderer Metalle sind aber weniger aktive Polykondensationskatalysatoren, erfordern höhere molare Mengen oder längere Reaktionszeiten bis zur Erreichung bestimmter Molgewichte, katalysieren Neben- oder Zersetzungsreaktionen stärker als Antimonverbindungen bzw. erfordern die Zugabe der genannten Phosphorverbindungen zur Desaktivierung.However, compounds of other metals are less active polycondensation catalysts, require higher molar amounts or longer reaction times until certain molecular weights are reached, catalyze side or decomposition reactions more strongly than antimony compounds or require the addition of the phosphorus compounds mentioned for deactivation.
Nun ist es auch bekannt, lösliche Titanverbindungen als Polykondensationskatalysatoren zu verwenden. Nach H. Zimmermann, Faserforschung u. Textiltechnik 13 Nr. 11 (1962), 481 bis 490 ist deren katalytische Aktivität den Antimonverbindungen vergleichbar und Nebenreaktionen sind wenig störend. Titanverbindungen haben aber den Nachteil, die Polykondensate gelbbraun zu verfärben, besonders bei Äthylenglykol als Bestandteil der Polyester.Now it is also known to use soluble titanium compounds as polycondensation catalysts. According to H. Zimmermann, Faserforschung u. Textile technology 13 No. 11 (1962), 481 to 490, their catalytic activity is comparable to the antimony compounds and side reactions are not very troublesome. However, titanium compounds have the disadvantage of turning the polycondensates yellow-brown, especially with ethylene glycol as a component of the polyesters.
Es bestand daher die Aufgabe, die durch Titankatalysatoren bewirkte Verfärbung der Polykondensate zu vermindern und nach Möglichkeit die Wirksamkeit von Titankatalysatoren zu steigern.The object was therefore to reduce the discoloration of the polycondensates caused by titanium catalysts and, if possible, to increase the effectiveness of titanium catalysts.
Gegenstand der Erfindung ist daher ein Verfahren zur Herstellung von Polyestern aus mehrfunktionellen Alkoholen und mehrbasischen Carbonsäuren und/oder deren Alkylestern und/oder deren Anhydriden in Gegenwart von katalytisch wirksamen Titanverbindungen, in Gegenwart von Verbindungen der phosphorigen Säure sowie ggf. weiteren bekannten Umesterungs-, Veresterungs- und Polykondensations-Katalysatoren und weiteren Hilfsstoffen, dadurch gekennzeichnet, dass als Verbindungen der phosphorigen Säure katalytische Mengen von Addukten aus phosphoriger Säure und Monoepoxiden mit Molverhältnissen der Komponenten von 1: 1, 1:2 oder 1:3 verwendet werden.The invention therefore relates to a process for the preparation of polyesters from polyfunctional alcohols and polybasic carboxylic acids and / or their alkyl esters and / or their anhydrides in the presence of catalytically active titanium compounds, in the presence of compounds of phosphorous acid and optionally other known transesterification, esterification - And polycondensation catalysts and other auxiliaries, characterized in that catalytic amounts of adducts of phosphorous acid and monoepoxides with molar ratios of the components of 1: 1, 1: 2 or 1: 3 are used as compounds of phosphorous acid.
Zwar sind aus EP-A 1 -6603 Triester der Phosphorsäure mit Glykolen und aus AT-B-263371 Polyester aus Glykolen und phosphoriger Säure als Stabilisatoren zur Verbesserung der Licht- bzw. Thermostabilität von Polyestern bekannt, jedoch ist dort nicht die Steigerung der Wirksamkeit von Titankatalysatoren bei der Polyesterbildung beschrieben.Triesters of phosphoric acid with glycols and from AT-B-263371 polyesters of glycols and phosphorous acid are known from EP-A 1 -6603 as stabilizers for improving the light and thermal stability of polyesters, but there is no increase in the effectiveness of Titanium catalysts described in the polyester formation.
Als Titankatalysatoren werden dabei an sich beliebige bekannte Titankatalysatoren verstanden, vorzugsweise Titanester aliphatischer oder cycloaliphatischer Alkohole mit 3 bis 12, insbesondere 4 bis 10 C-Atomen wie Butyltitanat und Octyltitanat, sowie lösliche Titan-Chelate aus beispielsweise 1,3-Diolen, insbesondere mit 2,2,4-Trimethylpentandiol--1,3, 2-Methylpentandiol-2,4 oder 2-Äthylhexandiol-1,3. Die zusätzlich zu den Titankatalysatoren verwendeten Addukte sind besonders für die Veresterungsstufe und in gleichem Masse für die anschliessende Polykondensationsstufe geeignet. Polyester von geringerem und besonders von hohem Polykondensationsgrad können mit ihrer Hilfe hergestellt werden.Titanium catalysts are understood to be any known titanium catalysts per se, preferably titanium esters of aliphatic or cycloaliphatic alcohols having 3 to 12, in particular 4 to 10, carbon atoms, such as butyl titanate and octyl titanate, and soluble titanium chelates made from, for example, 1,3-diols, in particular with 2 , 2,4-trimethylpentanediol - 1,3, 2-methylpentanediol-2,4 or 2-ethylhexanediol-1,3. The adducts used in addition to the titanium catalysts are particularly suitable for the esterification stage and to the same extent for the subsequent polycondensation stage. With their help, polyesters of low and particularly high degree of polycondensation can be produced.
Die Addukte erlauben es, anstelle von stark verfärbten Polyestern hellfarbige Polyester mit sehr niedrigen Farbzahlen herzustellen.The adducts make it possible to produce light-colored polyesters with very low color numbers instead of highly discolored polyesters.
Überraschend steigern die Addukte die Wirksamkeit der Titankatalysatoren, so dass die Reaktionszeit der Veresterung mit steigender Menge der Addukte und mit steigender Menge der EpoxiQ8 im Addukt teilweise stark verkürzt wird, der Kondensa- , tionsgrad erhöht wird und die Vollständigkeit der Reaktion, messbar an verminderten Carboxyzahlen, Säurezahlen bzw. Hydroxylzahlen, gesteigert wird. Von besonderem Wert ist eine Absenkung der Säurezahlen im fertigen Polyester auf sehr geringe Werte.Surprisingly, the adducts increase the effectiveness of the titanium catalysts, so that the reaction time of the esterification is sometimes greatly shortened with increasing amount of adducts and with increasing amount of EpoxiQ8 in the adduct, the degree of condensation is increased and the completeness of the reaction, measurable with reduced carboxy numbers , Acid numbers or hydroxyl numbers, is increased. Of particular value is a reduction in the acid numbers in the finished polyester to very low values.
In der Polykondensationsstufe bewirken die Addukte eine deutliche, zum Teil sehr erhebliche Erhö- . hung der Viskosität und damit des Molargewichts, wobei erhöhte Viskositäten teils durch erhöhten Zusatz der Addukte, besonders aber durch erhöhte Mengen Monoepoxid im Addukt erzielt werden. Die Addukte werden daher bevorzugt in der Veresterungsstufe und nachfolgend in der Polykondensa- ;- tionsstufe eingesetzt und ermöglichen somit, zusammen mit der Titanverbindung allein in der gegebenenfalls vorangehenden Umesterungsstufe, die Verwendung eines einzigen Katalysators für die gesamte Polyesterherstellung.In the polycondensation stage, the adducts cause a significant, sometimes very significant increase. The viscosity and thus the molar weight, increased viscosities being achieved in part by increased addition of the adducts, but especially by increased amounts of monoepoxide in the adduct. The adducts are therefore preferably used in the esterification stage and subsequently in the polycondensation stage and thus make it possible to together with the titanium compound alone in the possibly preceding transesterification stage, the use of a single catalyst for the entire polyester production.
Die Veresterung in der Veresterungsstufe ist wesentlich vollständiger als bisher erreichbar, gemessen am abdestillierten Wasser, bevor durch Temperaturerhöhung und Druckverminderung die Polykondensation eingeleitet wird.The esterification in the esterification stage is much more complete than before, measured on the distilled water, before the polycondensation is initiated by increasing the temperature and reducing the pressure.
Die Menge der Addukte kann je 0,001 g Titankatalysator 0,2 bis 1,8g, vorzugsweise 0,3 bis 1, 5 g, Addukt betragen.The amount of adducts can be 0.2 to 1.8 g, preferably 0.3 to 1.5 g, of adduct per 0.001 g of titanium catalyst.
Die Herstellung der Addukte kann in inerten Lösungsmitteln, vorzugsweise jedoch lösungsmittelfrei, erfolgen, wobei das jeweilige Monoepoxid unter Stickstoffatmosphäre in einem Rundkolben mit aufgesetzter Kolonne unter Rühren auf Temperaturen bis 200°C, vorzugsweise auf 70 bis 100°C, erwärmt wird. Die Zugabe der phosphorigen Säure, vorzugsweise als 99%ige phosphorige Säure, erfolgt in Portionen oder kontinuierlich, wobei wegen exothermer Reaktionen erforderlichenfalls zu kühlen ist. Eine Nachreaktionszeit bei Temperaturen von 60 bis 90° kann sich anschliessen.The adducts can be prepared in inert solvents, but preferably without solvents, the particular monoepoxide being heated to temperatures of up to 200 ° C., preferably 70 to 100 ° C., in a round-bottomed flask with a column attached, under a nitrogen atmosphere. The phosphorous acid, preferably as 99% phosphorous acid, is added in portions or continuously, cooling being necessary if necessary due to exothermic reactions. A post-reaction time at temperatures of 60 to 90 ° can follow.
Addukte mit Molverhältnissen von phosphoriger Säure und Monoepoxid von 1:1,1:2 oder 1:3 werden hergestellt und verwendet. Als Monoepoxide kommen beliebige bekannte Monoepoxide infrage, insbesondere die Glycidylester aliphatischer oder cycloaliphatischer Carbonsäuren, die Glycidyläther von Monoalkoholen und ggf. Alkylphenolen sowie Alkenoxide und ggf. Cycloalkenoxide mit bevorzugt 5 bis 10 C-Atomen.Adducts with molar ratios of phosphorous acid and monoepoxide of 1: 1.1: 2 or 1: 3 are produced and used. Any known monoepoxides are suitable as monoepoxides, in particular the glycidyl esters of aliphatic or cycloaliphatic carboxylic acids, the glycidyl ethers of monoalcohols and optionally alkylphenols, and also alkene oxides and optionally cycloalkene oxides with preferably 5 to 10 carbon atoms.
Monoepoxide mit relativ hochliegenden Siedepunkten werden bevorzugt.Monoepoxides with relatively high boiling points are preferred.
Bevorzugte Epoxide sind Glycidylester von Fettsäuren mit 6 bis 15 C-Atomen. Der Glycidylester aus verzweigtkettigen gesättigten Fettsäuren eines Gemisches mit 8 bis 10 C-Atomen wird in den Beispielen kurz «PC» unter Hinzufügung der Molverhältnisse genannt («Cardura E.»@ Shell).Preferred epoxides are glycidyl esters of fatty acids with 6 to 15 carbon atoms. The glycidyl ester from branched-chain saturated fatty acids of a mixture with 8 to 10 carbon atoms is briefly referred to in the examples as “PC” with the addition of the molar ratios (“Cardura E.” @ Shell).
Weiter bevorzugt sind Glycidyläther aus gesättigten aliphatischen Alkoholen mit 4 bis 6 C-Atomen, und Alkenoxide, d.h. Epoxide aus geradkettigen aliphatischen Alkenen mit beliebiger Lage der Doppelbindung mit 8 bis 12 C-Atomen.Glycidyl ethers of saturated aliphatic alcohols having 4 to 6 carbon atoms and alkene oxides, i.e. Epoxides from straight-chain aliphatic alkenes with any position of the double bond with 8 to 12 carbon atoms.
Die Komponenten der verfahrensgemäss hergestellten Mischpolyester können alle bekannten aliphatischen, cycloaliphatischen bzw. aromatischen Diole, ggf. Triole und Polyole sowie aliphatische, cycloaliphatische bzw. aromatische Dicarbonsäuren sowie ggf. Tri- und Polycarbonsäuren sowie deren Derivate, insbesondere deren Ester von Ci- bis C4-Alkoholen sowie deren Anhydride umfassen.The components of the mixed polyesters produced according to the process can contain all known aliphatic, cycloaliphatic or aromatic diols, if appropriate triols and polyols, and aliphatic, cycloaliphatic or aromatic dicarboxylic acids as well as if appropriate tri- and polycarboxylic acids and their derivatives, in particular their esters of Ci to C 4 -Alcohols and their anhydrides include.
Der erreichte Polykondensationsgrad wird als reduzierte Viskosität 11 red. = η rel. -1 bei der Konzentration von 1 g Polymer in 100 ml Lösung aus Phenol und 2,2,4,4-Tetrachloräthan im Gewichtsverhältnis 3:2 bei 25°C gemessen.The degree of polycondensation achieved is reduced as a reduced viscosity 11 red. = η rel. -1 measured at a concentration of 1 g polymer in 100 ml solution of phenol and 2,2,4,4-tetrachloroethane in a weight ratio of 3: 2 at 25 ° C.
Die Bestimmung des Schmelzpunkt-Peaks (Ts) des Rekristallisations-Peaks (TR) und des Glaspunktes (TG) wurde mit einem Differentialkalorimeter, Mod. DSC 1 der Fa. Perkin-Elmer, durchgeführt.The melting point peak (Ts), the recrystallization peak (T R ) and the glass point (TG) were determined using a differential calorimeter, model DSC 1 from Perkin-Elmer.
Die Endgruppenkonzentration wird durch Säurezahl SZ, Hydroxylzahl OHZ, beide in mg KOH/g, bzw. die Carboxylzahl (C) in mVaLCOOH/kg Polymer nach H. Pohl, Analytic. Chem. 26 (1954), 1614, gemessen.The end group concentration is determined by acid number SZ, hydroxyl number OHZ, both in mg KOH / g, or the carboxyl number (C) in mVaLCOOH / kg polymer according to H. Pohl, Analytic. Chem. 26 (1954), 1614.
Die Gardner-Farbzahl (GFZ) der fliessfähigen oder geschmolzenen Polyester wurde nach DIN 6961 bestimmt.The Gardner color number (GFZ) of the flowable or melted polyester was determined in accordance with DIN 6961.
In den Beispielen 1 bis 12 sowie im Vergleichsbeispiel A wurden die Bedingungen der eigentlichen Polykondensation mit 4 Stunden bei 270°C bei Vakuum von 0,1 mbar gleichgehalten, um den Einfluss der Addukte auf Zersetzung und Verfärbung anhand der Farbzahl unter gleicher und in der Praxis vielfach auftretender vergleichsweise hoher Temperaturbelastung zu zeigen. Ebenfalls aus Gründen der Vergleichbarkeit wurde überwiegend als Katalysator Tetrabutyltitanat verwendet, obgleich weitere lösliche Titankatalysatoren in gleichem Masse verwendet werden können.In Examples 1 to 12 and in Comparative Example A, the conditions of the actual polycondensation were kept the same for 4 hours at 270 ° C. under a vacuum of 0.1 mbar in order to determine the influence of the adducts on decomposition and discoloration based on the color number under the same and in practice to show frequently occurring comparatively high temperature loads. Also for reasons of comparability, tetrabutyl titanate was predominantly used as the catalyst, although other soluble titanium catalysts can be used to the same extent.
97 g Dimethylterephthalat, 40,73 g Äthylenglykol, 60,63 g Neopentylglykol und 0,0082 g Butyltitanat wurden unter Reinstickstoff sowie unter Rühren in 3 Std. bei 160-190°C umgeestert, wobei 40 ml Methanol abdestilliert worden waren. Sodann wurden 83 g Isophthalsäure und 0,485 g = 0,0016 Mol Addukt PC 1:1 zugesetzt. Dadurch kühlte das Umesterungsprodukt auf = 160°C ab. Der Kolbeninhalt wurde nun innerhalb von 150 Min. auf 180°C aufgeheizt, wobei zugleich 18 ml Wasser abdestillierten. Danach wurde die Temperatur im Verlauf von 1,5 Std. auf 270°C erhöht und zugleich der Druck innerhalb dieser Zeit auf 0,1 mbar erniedrigt. Nach weiteren 4 Std. unter diesen Bedingungen wurde die Polykondensation durch Aufheben des Vakuums beendet. Das so erhaltene Produkt wies folgende Kennzahlen auf:
Es wurde wie in Beispiel 1 in Gegenwart von 0,0082 g Butyltitanat verfahren, jedoch das Addukt PC 1:1 durch 0,0016 Mol = 0,496 g Triphenylphosphit ersetzt. Das so erhaltene Produkt hatte folgende Kennzahlen:
Es wurde wie in Beispiel 1 verfahren, wobei das PC 1:1 1 = 0,0016 Mol durch a) 0,842 g PC 1:2 = 0,0016 Mol bzw. b) 1,225 g PC 1:3 = 0,0016 Mol, ersetzt wurde.The procedure was as in Example 1, the PC 1: 1 1 = 0.0016 mol by a) 0.842 g PC 1: 2 = 0.0016 mol or b) 1.225 g PC 1: 3 = 0.0016 mol, was replaced.
Die so erhaltenen Produkte hatten folgende Kennzahlen:
106,7 g Dimethylterephthalat, 80,6g Äthylenglykol und 0,0082 g Butyltitanat wurden wie in Beispiel 1 umgeestert. Dabei fielen 44 ml Methanol an. Sodann wurden 84,6 g Azelainsäure und 0,485 g = 0,0016 Mol PC 1:1 zugesetzt und wie in Beispiel 1 verestert, wobei 16,2 ml Wasser abdestillierten. Danach wurde wie in Beispiel 1 polykondensiert. Das Produkt hatte die Kennzahlen: η red. 0,95, TG -5°C, C 19 und GFZ 3.106.7 g of dimethyl terephthalate, 80.6 g of ethylene glycol and 0.0082 g of butyl titanate were transesterified as in Example 1. 44 ml of methanol were obtained. Then 84.6 g of azelaic acid and 0.485 g = 0.0016 mol of PC 1: 1 were added and esterified as in Example 1, 16.2 ml of water being distilled off. Thereafter, polycondensation was carried out as in Example 1. The product had the key figures: η red. 0.95, TG -5 ° C, C 19 and GFZ 3.
Es wurde wie in Beispiel 3 verfahren, wobei das PC 1:1 1 = 0,0016 Mol durch folgende Addukte ersetzt wurde:
- a) 0,842 g PC 1:2 = 0,0016 Mol
- b) 1,225 g PC 1:3 = 0,0016 Mol.
- a) 0.842 g PC 1: 2 = 0.0016 mol
- b) 1.225 g PC 1: 3 = 0.0016 mol.
Die so erhaltenen Produkte hatten folgende Kennzahlen:
116,4 g Dimethylterephthalat, 45,88 g Äthylenglykol, 66,24 g Cyclohexandimethanol und 0,0082 g Butyltitanat wurden wie in Beispiel 1 umgeestert, wobei 48 ml Methanol abdestillierten. Danach wurden 66,4 g Terephthalsäure und 0,485 g = 0,0016 Mol PC 1:1 zugesetzt und wie in Beispiel 1 verestert, wobei 14 ml Wasser abdestillierten. Wie in Beispiel 1 wurde danach polykondensiert. Das Produkt hatte die Kennzahlen: red. 0,89, TG 84°C, C 31 und GFZ 2.116.4 g of dimethyl terephthalate, 45.88 g of ethylene glycol, 66.24 g of cyclohexanedimethanol and 0.0082 g of butyl titanate were transesterified as in Example 1, 48 ml of methanol being distilled off. Then 66.4 g of terephthalic acid and 0.485 g = 0.0016 mol of PC 1: 1 were added and esterified as in Example 1, 14 ml of water being distilled off. As in Example 1, polycondensation was then carried out. The product had the key figures: red. 0.89, TG 84 ° C, C 31 and GFZ 2.
Es wurde wie in Beispiel 5 verfahren, wobei das PC 1:1 = 0,0016 Mol durch a) 0,842 g PC 1:2 = 0,0016 Mol bzw. b) 1,225 g PC 1:3 = 0,0016 Mol ersetzt wurde.The procedure was as in Example 5, the PC 1: 1 = 0.0016 mol being replaced by a) 0.842 g PC 1: 2 = 0.0016 mol or b) 1.225 g PC 1: 3 = 0.0016 mol .
Die so erhaltenen Produkte hatten folgende Kennzahlen:
33,2 Isophthalsäure, 116,8 g Adipinsäure, 52,08 g Äthylenglykol, 38,94 g Hexandiol-1,6, 0,0082 g Butyltitanat und 0,485 g = 0,0016 Mol PC 1:1 1 wurden unter Reinstickstoff sowie unter Rühren innerhalb von 190 Minuten bei 160-180°C verestert, wonach 36 ml Wasser abdestilliert waren. Danach wurde wie in Beispiel 1 die Polykondensation durchgeführt. Das so erhaltene Produkt hatte die Kennzahlen: red. 0,663, TG -51 °C, C 35 und GFZ 4.33.2 isophthalic acid, 116.8 g adipic acid, 52.08 g ethylene glycol, 38.94 g 1,6-hexanediol, 0.0082 g butyl titanate and 0.485 g = 0.0016 mol PC 1: 1 1 were under pure nitrogen and under Stirring esterified at 160-180 ° C within 190 minutes, after which 36 ml of water were distilled off. The polycondensation was then carried out as in Example 1. The product obtained in this way had the key figures: red. 0.663, TG -51 ° C, C 35 and GFZ 4.
Es wurde wie in Beispiel 7 verfahren, wobei das PC 1:1 = 0,0016 Mol durch a) 0,842 g PC 1:1 = 0,0016 Mol und b) 1,225 g PC 1:3 = 0,0016 Mol ersetzt wurde.The procedure was as in Example 7, the PC 1: 1 = 0.0016 mol being replaced by a) 0.842 g PC 1: 1 = 0.0016 mol and b) 1.225 g PC 1: 3 = 0.0016 mol.
Die so erhaltenen Produkte hatten folgende Kennzahlen:
135,8 g Dimethylterephthalat, 97,2 g Butandiol--1,4, 9,99 g Äthylenglykol, 16,77 g Neopentylglykol und 0,0082 g Butyltitanat wurden wie in Beispiel 1 umgeestert, wobei 56 ml Methanol anfielen. Danach wurden 60,65 g Sebacinsäure und 0,485 g = 0,0016 Mol PC 1:1 zugesetzt und wie in Beispiel 1 verestert; hierbei destillierten 10,8 ml Wasser über. Sodann wurde wie in Beispiel 1 polykondensiert. Das Produkt hatte die Kennzahlen: η red. 1,67 , Ts 153°C, TR 80°C, C 14 und GFZ 3-4.135.8 g of dimethyl terephthalate, 97.2 g of 1,4-butanediol, 9.99 g of ethylene glycol, 16.77 g of neopentyl glycol and 0.0082 g of butyl titanate were transesterified as in Example 1, 56 ml of methanol being obtained. Then 60.65 g of sebacic acid and 0.485 g = 0.0016 mol of PC 1: 1 were added and esterified as in Example 1; 10.8 ml of water distilled over. The mixture was then polycondensed as in Example 1. The product had the key figures: η red. 1.67, T s 153 ° C, T R 80 ° C, C 14 and GFZ 3-4.
Es wurde wie in Beispiel 9 verfahren, wobei das PC 1:1 = 0,0016 Mol durch a) 0,842 g PC 1:2 = 0,0016 Mol und b) 1,225 g PC 1:3 = 0,0016 Mol ersetzt wurde.The procedure was as in Example 9, the PC 1: 1 = 0.0016 mol being replaced by a) 0.842 g PC 1: 2 = 0.0016 mol and b) 1.225 g PC 1: 3 = 0.0016 mol.
Die so erhaltenen Produkte hatten folgende Kennzahlen:
126,1 g Dimethylterephthalat, 99,0 g Butandiol--1,4, 38,46 g Tripropylenglykol und 0,0082 g Butyltitanat wurden wie in Beispiel 1 umgeestert, wobei 52 ml Methanol anfielen. Danach wurden 51,1 g Adipinsäure und 0,485 g = 0,0016 Mol PC 1:1 zugesetzt und wie in Beispiel 1 verestert. Dabei destillierten 12,6 ml Wasser über. Danach wurde wie in Beispiel 1 polykondensiert. Das Produkte hatte die Kennzahlen: η red. 0,78, Ts 137°C, TR 70°C, C 34 und GFZ 4.126.1 g of dimethyl terephthalate, 99.0 g of 1,4-butanediol, 38.46 g of tripropylene glycol and 0.0082 g of butyl titanate were transesterified as in Example 1, 52 ml of methanol being obtained. Then 51.1 g of adipic acid and 0.485 g = 0.0016 mol of PC were added 1: 1 and esterified as in Example 1. 12.6 ml of water distilled over. Thereafter, polycondensation was carried out as in Example 1. The product had the key figures: η red. 0.78, T s 137 ° C, T R 70 ° C, C 34 and GFZ 4.
Es wurde wie in Beispiel 11 verfahren, wobei das PC 1:1 1 = 0,0016 Mol durch a) 0,842 g PC 1:2 = 0,0016 Mol, b) 1,225 g PC 1:3 = 0,0016 Mol ersetzt wurde.The procedure was as in Example 11, the PC 1: 1 1 = 0.0016 mol being replaced by a) 0.842 g PC 1: 2 = 0.0016 mol, b) 1.225 g PC 1: 3 = 0.0016 mol .
Die so erhaltenen Produkte hatten folgende Kennzahlen:
67,5 g Butandiol und 222 g Phthalsäureanhydrid wurden unter Reinstickstoff sowie unter Rühren 50 Min. bei 90-100°C gehalten, wobei sich Butylendiphthalat mit einer SZ von 295 mg KOH/g bildete. Danach wurden 0,195 g Butyltitanat, 31 9 Äthylenglykol, 56,18 g Diäthylenglykol, 185, 12 Neopentylglykol, 43,8 g Adipinsäure und 199,2 g Isophthalsäure zugesetzt. Der Kolbeninhalt wurde nun innerhalb von 4 Std. auf 220°C geheizt, wobei zugleich 78 ml Wasser überdestillierten. Bei 220°C wurde nach 30 Minuten ein Vakuum von 300 mbar angelegt und danach innerhalb von 2 Std. auf 8 mbar gesenkt. Nach 1 Std. unter diesen Bedingungen wurde die Kondensation beendet. Das Produkt hatte die Kennzahlen: η red. 0,270, SZ 16, OHZ 32 und GFZ 12-13.67.5 g of butanediol and 222 g of phthalic anhydride were kept under pure nitrogen and with stirring at 90-100 ° C. for 50 minutes, with butylene diphthalate having an AN of 295 mg KOH / g. Then 0.195 g of butyl titanate, 31 9 ethylene glycol, 56.18 g diethylene glycol, 185, 12 neopentyl glycol, 43.8 g adipic acid and 199.2 g isophthalic acid were added. The contents of the flask were then heated to 220 ° C. in the course of 4 hours, during which time 78 ml of water distilled over. A vacuum of 300 mbar was applied at 220 ° C. after 30 minutes and then reduced to 8 mbar within 2 hours. After 1 hour under these conditions, the condensation was stopped. The product had the key figures: η red. 0.270, SZ 16, OHZ 32 and GFZ 12-13.
Es wurde wie in Vergleichsbeispiel B verfahren, wobei folgende Addukte in der Veresterungsreaktionsstufe zugesetzt wurden: a) PC 1:1 = 0,036 Mol, b) PC 1:2 = 0,036 Mol, c) PC 1:3 = 0,036 Mol.The procedure was as in Comparative Example B, the following adducts being added in the esterification reaction stage: a) PC 1: 1 = 0.036 mol, b) PC 1: 2 = 0.036 mol, c) PC 1: 3 = 0.036 mol.
Die so erhaltenen Produkte hatten folgende Kennzahlen:
99,6 g Isophthalsäure, 355,2 g Phthalsäureanhydrid, 108,0 g Butandiol-1,4, 169,52 g Neopentylglykol, 45,26 g Äthylenglykol und 0,195 g Butyltitanat wurden innerhalb von 5 Std. unter Reinstickstoff und Rühren auf 220°C aufgeheizt. Dabei destillierten 62 ml Wasser über. Danach wurde ein Vakuum von 200 mbar angelegt. Nach 2,5 Std. unter diesen Bedingungen wurde die Kondensation beendet.99.6 g of isophthalic acid, 355.2 g of phthalic anhydride, 108.0 g of 1,4-butanediol, 169.52 g of neopentyl glycol, 45.26 g of ethylene glycol and 0.195 g of butyl titanate were brought to 220 ° within 5 hours with pure nitrogen and stirring C. heated up. 62 ml of water distilled over. A vacuum of 200 mbar was then applied. After 2.5 hours under these conditions, the condensation was stopped.
Das erhaltene Produkt hatte folgende Kennzahlen: η red. 0,225, SZ 18, OHZ 37 und GFZ 9.The product obtained had the following key figures: η red. 0.225, SZ 18, OHZ 37 and GFZ 9.
Es wurde wie in Vergleichsbeispiel C verfahren, wobei in der Veresterungsreaktionsstufe: a) PC 1:1 1 = 0,036 Mol, b) PC 1:2 = 0,036 Mol, c) PC 1:3 = 0,036 Mol zugesetzt wurden.The procedure was as in Comparative Example C, the following being added in the esterification reaction step: a) PC 1: 1 1 = 0.036 mol, b) PC 1: 2 = 0.036 mol, c) PC 1: 3 = 0.036 mol.
Die so erhaltenen Produkte hatten folgende Kennzahlen:
Es wurde wie in Vergleichsbeispiel B verfahren, wobei folgende Addukte in der Veresterungsstufe zugesetzt wurden: a) Addukt aus phosphoriger Säu- re/Dodecen-1-oxid (im folgenden als PD bezeichnet) im Molverhältnis 1:1 = 0,036 Mol, b) 1:2 = 0,036 Mol und c) 1:3 = 0,036 Mol.The procedure was as in Comparative Example B, the following adducts being added in the esterification stage: a) adduct of phosphorous acid / dodecen-1-oxide (hereinafter referred to as PD) in a molar ratio of 1: 1 = 0.036 mol, b) 1 : 2 = 0.036 mol and c) 1: 3 = 0.036 mol.
Die so erhaltenen Produkte hatten folgende Kennzahlen:
Es wurde wie in Vergleichsbeispiel B verfahren, wobei in der Veresterungsstufe a) das Addukt aus phosphoriger Säure/n-Butylglycidyläther (als PB bezeichnet) im Mol-Verhältnis 1:1 = 0,036 Mol b) PB im Mol-Verhältnis 1:2 = 0,036 Mol und c) PB im Mol-Verhältnis 1:3 = 0,036 Mol zugesetzt wurden.The procedure was as in Comparative Example B, but in the esterification stage a) the adduct of phosphorous acid / n-butylglycidyl ether (referred to as PB) in a molar ratio of 1: 1 = 0.036 mol b) PB in a molar ratio of 1: 2 = 0.036 Mol and c) PB in the molar ratio 1: 3 = 0.036 mol were added.
Die so erhaltenen Produkte hatten folgende Kennzahlen:
Claims (1)
- Process for the production of polyesters from polyfunctional alcohols and polyfunctional carboxylic acids and/or alkyl esters and/or anhydrides thereof in the presence of catalytically active titanium compounds, in the presence of compounds of phosphorous acid as well as optionally further known trans-esterification, esterification and polycondensation catalysts and further auxiliary substances, characterised in that, as compounds of phosphorous acids, there are used catalytic amounts of adducts of phosphorous acid and monoepoxides with molar ratios of the components of 1:1, 1:2 or 1:3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT83112290T ATE22695T1 (en) | 1983-01-07 | 1983-12-07 | PROCESS FOR THE PRODUCTION OF LIGHT COLORED POLYESTERS USING TITANIUM CATALYSTS. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3300315 | 1983-01-07 | ||
| DE19833300315 DE3300315A1 (en) | 1983-01-07 | 1983-01-07 | METHOD FOR PRODUCING LIGHT-COLORED POLYESTERS USING TITANIUM CATALYSTS |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0117912A1 EP0117912A1 (en) | 1984-09-12 |
| EP0117912B1 true EP0117912B1 (en) | 1986-10-08 |
Family
ID=6187823
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP83112290A Expired EP0117912B1 (en) | 1983-01-07 | 1983-12-07 | Process for producing lightly coloured polyesters by using titanium catalysts |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4482700A (en) |
| EP (1) | EP0117912B1 (en) |
| JP (1) | JPS59136325A (en) |
| AT (1) | ATE22695T1 (en) |
| CA (1) | CA1201245A (en) |
| DE (2) | DE3300315A1 (en) |
Families Citing this family (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NO167393C (en) * | 1984-05-14 | 1991-10-30 | Kenrich Petrochemicals | ANY SUBSTITUTED NEOAL COCOY COMPOUNDS AND THEIR USE. |
| US4657988A (en) * | 1985-04-22 | 1987-04-14 | Kenrich Petrochemicals, Inc. | Repolymerization |
| JPH0826122B2 (en) * | 1992-04-02 | 1996-03-13 | ピーピージー インダストリーズ，インコーポレイテッド | Epoxide-phosphorus containing acid-cyclic anhydride reaction products and their use in coating compositions |
| US5453479A (en) * | 1993-07-12 | 1995-09-26 | General Electric Company | Polyesterification catalyst |
| US5760161A (en) * | 1997-02-10 | 1998-06-02 | Albemarle Corporation | Process for making unsaturated, thermosetting, brominated phthalic anhydride/polyol polyester resins |
| US6255441B1 (en) | 1998-04-17 | 2001-07-03 | E. I. Du Pont De Nemours And Company | Titanium-containing catalyst composition and processes therefor and therewith |
| US6075115A (en) * | 1999-10-19 | 2000-06-13 | E. I. Du Pont De Nemours And Company | Process for the production of 5-sulfo isophthalate bis-glycolate ester metal salts and oxysulfonated polyesters made therefrom |
| US6166170A (en) * | 1999-12-02 | 2000-12-26 | E. I. Du Pont De Nemours And Company | Esterification catalysts and processes therefor and therewith |
| KR20020063208A (en) * | 1999-12-10 | 2002-08-01 | 다우 글로벌 테크놀로지스 인크. | Catalyst systems for polycondensation reactions |
| US6712234B2 (en) * | 2000-02-14 | 2004-03-30 | Ti Group Automotive Systems Technology Center Gmbh | Fuel tank and method for its production |
| US6303738B1 (en) | 2000-08-04 | 2001-10-16 | E. I. Du Pont De Nemours And Company | Esterification process |
| MXPA04011110A (en) * | 2002-05-09 | 2005-07-14 | Equipolymers Gmbh | Catalyst systems for polycondensation reactions. |
| US6863982B2 (en) * | 2002-10-11 | 2005-03-08 | Ppg Industries Ohio, Inc. | Curable film-forming composition exhibiting improved yellowing resistance |
| CN101981083B (en) | 2008-03-28 | 2013-07-10 | 伊科聚合物股份有限公司 | A new titanium-based catalyst showing excellent activity and selectivity in polycondensation reactions |
| US8877862B2 (en) | 2011-07-15 | 2014-11-04 | Saudi Basic Industries Corporation | Method for color stabilization of poly(butylene-co-adipate terephthalate |
| US9334360B2 (en) | 2011-07-15 | 2016-05-10 | Sabic Global Technologies B.V. | Color-stabilized biodegradable aliphatic-aromatic copolyesters, methods of manufacture, and articles thereof |
| US8933162B2 (en) | 2011-07-15 | 2015-01-13 | Saudi Basic Industries Corporation | Color-stabilized biodegradable aliphatic-aromatic copolyesters, methods of manufacture, and articles thereof |
| US8946345B2 (en) | 2011-08-30 | 2015-02-03 | Saudi Basic Industries Corporation | Method for the preparation of (polybutylene-co-adipate terephthalate) through the in situ phosphorus containing titanium based catalyst |
| US8901273B2 (en) | 2012-02-15 | 2014-12-02 | Saudi Basic Industries Corporation | Amorphous, high glass transition temperature copolyester compositions, methods of manufacture, and articles thereof |
| US8889820B2 (en) | 2012-02-15 | 2014-11-18 | Saudi Basic Industries Corporation | Amorphous, high glass transition temperature copolyester compositions, methods of manufacture, and articles thereof |
| US8969506B2 (en) | 2012-02-15 | 2015-03-03 | Saudi Basic Industries Corporation | Amorphous, high glass transition temperature copolyester compositions, methods of manufacture, and articles thereof |
| US8895660B2 (en) | 2012-03-01 | 2014-11-25 | Saudi Basic Industries Corporation | Poly(butylene-co-adipate terephthalate), method of manufacture, and uses thereof |
| US9034983B2 (en) | 2012-03-01 | 2015-05-19 | Saudi Basic Industries Corporation | Poly(butylene-co-adipate terephthalate), method of manufacture and uses thereof |
| US8901243B2 (en) | 2012-03-30 | 2014-12-02 | Saudi Basic Industries Corporation | Biodegradable aliphatic-aromatic copolyesters, methods of manufacture, and articles thereof |
| CN110092897B (en) * | 2019-03-28 | 2021-03-26 | 北京化工大学 | Method for synthesizing polyether ester by catalysis of binary composite catalyst |
| CN113087889A (en) * | 2021-05-28 | 2021-07-09 | 华东理工大学 | Method for efficiently preparing poly (1, 4-cyclohexanedimethanol terephthalate) (PCT) |
Family Cites Families (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD45278A (en) * | ||||
| AT263371B (en) * | 1964-01-28 | 1968-07-25 | Engels Chemiefaserwerk Veb | Process for the production of high molecular weight polyesters or mixed polyesters, in particular those based on polyethylene terephthalate |
| AT251291B (en) * | 1964-09-07 | 1966-12-27 | Chemiefaser Lenzing Ag | Process for the production of fiber and film-forming polyesters |
| AT259232B (en) * | 1965-04-13 | 1968-01-10 | Chemiefaser Lenzing Ag | Process for the production of fiber and film-forming polyesters |
| US3441540A (en) * | 1965-06-28 | 1969-04-29 | Engels Chemiefaserwerk Veb | Method for the production of highmolecular polyesters or co-polyesters |
| US4082724A (en) * | 1968-12-03 | 1978-04-04 | Imperial Chemical Industries Limited | Production of aromatic polyesters of improved color |
| DE2206563A1 (en) * | 1972-02-11 | 1973-08-16 | Budalakk Festek Es Mugyantagya | Polyester resin prodn - using phosphates as combined modifiers and accelerators |
| JPS48101485A (en) * | 1972-04-04 | 1973-12-20 | ||
| DE2412216B2 (en) * | 1974-03-14 | 1979-12-13 | Davy International Ag, 6000 Frankfurt | Process for the production of linear polyesters |
| DE2523910C3 (en) * | 1975-05-30 | 1981-04-16 | Hoechst Ag, 6000 Frankfurt | New organic phosphites and their use as stabilizers |
| JPS5257291A (en) * | 1975-11-05 | 1977-05-11 | Teijin Ltd | Production of polyester |
| CH594006A5 (en) * | 1976-02-02 | 1977-12-30 | Ciba Geigy Ag | |
| DE2626827C2 (en) * | 1976-06-15 | 1986-07-31 | Bayer Ag, 5090 Leverkusen | Stabilization of polyethylene terephthalates |
| JPS6017333B2 (en) * | 1978-02-06 | 1985-05-02 | 株式会社日立製作所 | Polyester manufacturing method |
| DE2828463C2 (en) * | 1978-06-29 | 1980-08-28 | Hoechst Ag, 6000 Frankfurt | Process for the production of linear, light-stabilized polyesters matted with TiO2 |
| JPS5556121A (en) | 1978-10-20 | 1980-04-24 | Teijin Ltd | Preparation of polyester |
| JPS5562922A (en) | 1978-11-06 | 1980-05-12 | Teijin Ltd | Preparation of polyester |
| JPS5612180A (en) * | 1979-07-11 | 1981-02-06 | Matsushita Electric Ind Co Ltd | Sound multiplex receiver |
| US4424140A (en) * | 1982-06-03 | 1984-01-03 | Union Carbide Corporation | Stabilization of polycondensation catalysts |
| JPH06292280A (en) * | 1993-03-31 | 1994-10-18 | Saginomiya Seisakusho Inc | Monitor controller |
-
1983
- 1983-01-07 DE DE19833300315 patent/DE3300315A1/en not_active Withdrawn
- 1983-12-07 DE DE8383112290T patent/DE3366693D1/en not_active Expired
- 1983-12-07 EP EP83112290A patent/EP0117912B1/en not_active Expired
- 1983-12-07 AT AT83112290T patent/ATE22695T1/en not_active IP Right Cessation
- 1983-12-29 US US06/566,711 patent/US4482700A/en not_active Expired - Lifetime
-
1984
- 1984-01-05 JP JP59000118A patent/JPS59136325A/en active Granted
- 1984-01-06 CA CA000444851A patent/CA1201245A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CA1201245A (en) | 1986-02-25 |
| JPS59136325A (en) | 1984-08-04 |
| DE3300315A1 (en) | 1984-07-12 |
| ATE22695T1 (en) | 1986-10-15 |
| JPH0521927B2 (en) | 1993-03-26 |
| US4482700A (en) | 1984-11-13 |
| DE3366693D1 (en) | 1986-11-13 |
| EP0117912A1 (en) | 1984-09-12 |
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